Process of recovering pure sodium carbonate monohydrate from brines



Patented Sept. 1, 1 942 UNITED STATES" PAT E NT OFFICE m g osss or 'aecovsamc PURE sopr- BRINE CASBBONATE MONOHYDRATE FROM Alexis c. Houghton, nuuetgoaut, assignor to Bosto FredericADakin,

n,,Mass., as trustee No Drawing. Application February 13', 1940, r Serial No. 318,748

"scum (cums) This invention relates to the recovery of pure sodium carbonate from-the brines .and deposits of Owens Lake and other similar alkali deposits which are contaminated with sodium sulphate In my co-pending application Serial No. 73,498,

filed April 9, 1936; pursuant to which U. S. Letters Patent No. 2,193,817 were granted to me on March 19, 1940,} have shown that although the transition point from theheptahydrate to the monohydrate in a saturated solution of sodium carbonate which is also saturated or substantially saturated. with sodium chloride is 235 0., at

which-temperature the solution contains 16.3%-

nazcoa, such solution can readily be supersaturated into the metastable field of the heptahydrate up to 31 C.'or so, at which temperature the concentration of sodium carbonateis 21% 11.9.2603. By seeding such a brine with crystals of sodium carbonate monohydrate, or by warming it up a few degrees above 31 C. to cause the spon-. taneous formation of nuclei of sodium carbonate monohydrate, this supersaturation is readily re;

leased, and when solubility-equilibrium has been reached ajcrop of pure sodium carbonate monohydrate is precipitated. The sodium carbonate content of the solution in this operation falls from 21% NaaCOa to. about 15.5% NaaCOaat a temperature of 31 C., or less it the temperature density.

local, or a small portion of the brine may be withdrawn from-the vat, heated to 40-45 C. to iorm monohydrate crystals, and then returned to the vatto seed the large body of supersaturated brine therein. The mixture is allowed to come to solubility equilibrium while being maintained at a.

temperature above 24 C. in a se'ttler oi the Dorr t pe; and the thickened monohydrate precipitate is drawn oil from the*"bottom'ot the settler to suitable filters or cen'trifugalawhere it is washed practically free'frorn'gadhering mother liquor, and thendried at moderate heat to anhydrous sodium carbonate. The mother liquor containing about 15.5% NazCOzris then re-saturated with sodium carbonate decahydrate and sodium chloride-containing salts from thelake and.v the. process I I J repeated.

My preferred method of operation, however, in

this process is to obtain a large stock of fairly pure crude decahydrate close to the-plant. as described in U 8. Letters Patent No, 1,853,275,

issued to me and James G. Miller. .In that patent we have described a method of obtaining such a stock of crude decahydrate capable of being re-' crystallized -or purified by other means, which consists in filling large storage ponds or crystallizing vats near to the-plant, and capable of being drained, with naturally occurring brines from the lake at the season of the year when they contain a maximum concentration of sodium carbonate and a minimum content of. sodium sulphate, and allowing 'such brines to crystallize out a large crop of sodium carbonate decahydrate, low in'sodium sulphate, by subjecting them to the winter temperatures" prevailing in the Owens Lake region.

- The mother liquor is then drained away from the 1 will now describe how such a. process may best be carried out in commercial operation.

The 21% NazCO; brine supersaturated with respect to monohydratemay be prepared by one 01 the several methods described in my co-pending application already mentioned, one of which is to pump from the lake to the plant a mixture of brine and salts containing an excess of the solid phases of sodium carbonate decahydrate or heptahydrate and sodium chloride necessary for the saturation, but free from sodium carbonate monohydrate, and then agitate themixture at a temperature of 31 C. .for a suflicient' length of time for the brine-to reach saturation up to 21% NazCOs, and then separate. the clear brine from the excess solids The precipitation of monohydrate in this clear 21% NazCO: brine is then started by seeding with monohydrate crystals; or by warming it up suificiently (40-45 C.) to start up the precipitation spontaneously; It

will be unnecessary to warm up all of the brine to start Precipitation. s uch warming up may be NaiCOgJOHaO 90.8to 85.5 NMSO4.10H:O 1.6to 3.4 manor .3to 1.0 NaCl 1.4to -2.0 Moisture 5.9to' 8.1

Total 100.0 100.0

vats as completely as possible, leaving a substantial crop of crude decahydrate, which may have a composition between the following ranges:

This material may be conveyed to the plant, or it may be melted .up with steam heat andpumped to the plant to saturate a brine up to 21% NaaCCh. Preferably, however, a face is opened up in the bed 01 decahydrate, which may have a depth of 5 feet or more, by means of a power shovel, and the brine under pressure from the lake or other source played against this face from suitable nozzles to "hydraulic" it into a suspen sion of brine and decahydrate. This mixture containing a suflicient excess of decahydrate crystals is pumped to the plant. In addition ,Per cent 1 there is pumped from the surface of the lakesnear the plant, a mixture of surface salts, such salts containing 80% or more of solid sodium chloride.

Should such surface salts contain crystals of sodium carbonate monoh'ydrate in the warmer weather, it will be necessary to get rid of these. This is done simply by adding enough water to the mixture of surface salts in the plant to, completely dissolve any monohydrate crystals, but not enough to dissolve all of the sodium chloride present. As these surface salts contain 80% or more of sodium chloride, a large excess of solid sodium chloride will remain undissolved. After decanting oil" the mother liquor containing the sodium carbonate in solution, the remaining sodium chlorideis ready for use. Enough of these sodium chloride containing salts free from monohydrate is added to the suspension of decahydrate crystals in the brine to maintain saturation insodium chloride. The whole mass is then agitated at a temperature of 28 to 31 C. until 19% t0 21% NaaCOa brine is obtained, and the excess salts settled out or filtered oil. The clear brine then has approximately the following composi- This clear brine at a temperature'of 31 C. is seeded with sodium carbonate monohydrate crystals to release-the supersaturation and to precipitate out sodium carbonate monohydrate, and the mixture allowed to'come to solubility equilibrium at around this temperature, or slightly higher if a larger yield of the mo'nohydrate is desired. As the mixture is rather "thin" in the amount of solids carried, a thickener of the Dorr type is preferably used for this operation. As this holds a large volume of liquid, necessitating a fairly long time in which the precipitate is in contact with the mother liquor, it would'serve the double purpose of allowing the mixture to come to solubility equilibrium with respect to monohydrate, and also more readily handled on a filter of the rotary type or on a centrifuge. The monohydrate, and also to thicken the precipitated monohydrate so that it could be more readily handled on a filter-of the rotary typeoron a centrifuge. The monohydrate is drawn from the bottom of the thickener to the filter, and washed on the filter with a limited amount of water until it is practically free from. adhering mother liquor impurities. The recovery of sodium carbonate in the washed monohydrate is over 30% of the NaaCO: contained in the 21% NazCO'z brine, and the composition of the mother liquor is approximately as follows:

Per cent NazCOa 15.5

Per cent N8.2B2O4 -4 3.4 Per cent NazSO4 2.4 .Per cent NaCl equivalent 13.0

further precipitation of monohydrate. The

' orable.

amount of mother liquor will build up in volume in this operation on account of the amount of water in the deca'hydrate, and it will thus be necessary to discard about 25% of this mother liquor at each re-cycling operation. Over a part of the year whencold weather prevails, from November to March, or about four months, this mother liquor discarded may be discharged into carbonate brine, which can be used as alreadydescribed; For the balance of the year the excess mother liquor would either be discharged to the lake or stored in empty decahydrate storage-vats to await the advent of cold weather again to reduce the amount of fresh brine to be pumped from the lake for the following season. For the year round operation the recovery of sodium carbonate of the decahydrate as pure monohydrate would be or better. i

- The washed mcnohydrate from'th'"fllters isdried to anhydrous soda ash in a suitable dryer, and the ash wouldc'ontaid-over 99% NazCOz,

be free fromsilica, boratesfor organicj coloring matter, and be a dense ash.

The crystallizing vats are filled with brine from the lake in the months of July, August, September, and part of October, which will range in composition somewhat as follows:

Specific gravity about 1.345 Per cent NaaCO: from 15.2 to 16.4 Per cent NazBz04 from ,3.0,to 2.8 Per centNa2SO4 from 2.2,t0, 1.8 Per cent NaCl equivalent from 1.4.2 to 13.9

The crystallizing vats are made-large enough to hold a years supply of decahy'drate for thedefour months mentioned as being the most fav In the spring and summer months the decahydrate in the crystallizing vats being exposed to dry air will eiiloresce on the surface, forming monohydrate, which material must of course be avoided in the saturating operation. This difficulty can be overcomeby melting up the decahydrate in its own water of crystallization. Any monohydrate present would be insoluble in the melted decahydrate, and could be settled out or filtered off in the plant before the saturating operation. Or in making the saturation the temperature could be lowered'sufliciently' below the transition'point of rnon'ohydrate to heptahydrate,

or below 23.6 C., and agitated'at this lowertem' perature for a suflicient; length'oftime to allow .the monohydrate to hydrate completely'to'the heptahydrate, and thenthe saturation up to 21% NazCO3 proceeded with. Or'the dificulty could be overcome mostsimply by adding tothe ,liquefied"decahydr'ate containing monohydrate crystals in suspension just enough water to effect'complete solution of themon'o'hydra'te.

This process is also applicable, butless econom ical, to a decahydrate containing much larger amounts of sodium sulphate. "In this case in making the saturation up to 21% NaiCOz at 31 C., suflicient time would be allowed for the reaction of sodium carbonate with sodium sul phate to form the double salt NazCOiZNazSOa according, to theprinciples outlined in U. S. Letters Patent No. 1,853,275. The double salt is fairtent of the clear brine ready for the monohy-. drate precipitation would be reduced to about 2.5% Nazsoi, which'is suificiently low so that 7 no sodium sulphate willbe thrown down when the monohydrate is finally precipitated. How ever if the brine from the lake is pumped in the months already mentioned, there would be no danger of encountering high sulphate brines such as would give a high percentage of sodium sulphate in the decahydrate in the crystallizing vats, as such high sulphate brines only occur in the lake in the colder weather, when they would not be used for crystallizing out decahydrate in the vats.

The recovery of the sodium carbonate originaL ly contained in the brine pumped from the lake to the crytsallizing vats as marketable soda ash in this process is over 50%. For instance, if high carbonate brines are pumped from the lake in the months mentioned, and then allowed to stay in the crystallizing vats before draining off the mother liquor until the temperature of the brine has fallen to C.a condition very readily obtained in the cold winter months-there will be about 80% of the sodium carbonate in the brine crytsallized out-as decahydrate. It has already been mentioned that the recovery of the sodium carbonate as soda ash from the decahydrate will be around 70% for the year round operation. The overall recovery as soda ash of the sodium carbonate of the brine originally pumped from the lake is therefore well over 50%, making the process thoroughly commercial.

What I claim is:

l. The method of preparing pure sodium carbonate monohydrate which consists in agitating Owens Lake brine with a mixture of salts containing an excess of the solid phases of sodium chloride and any form of the normal sodium g or from 19% to 21% N21200:, is saturated with] carbonate except sodium carbonate mono-,

V um carbonate monohydrate by raising the temperature of at least a portion of the brine to a temperature sufiiciently above 31 centigrade to cause it to spontaneously separate out sodium carbonate monohydrate, maintaining the mixture at a temperature over 24 c'entigrade for a sumcien't length of.time to come to solubility equilibrium with respect to the monohydrate, separating the precipitated .puremonohydrate from the mother liquor, and washing same substantially free from adhering mother liquor impurities.

2. The methodoi preparing pure sodium carbonate monohydrate which consists in agitating Owens Lake brine with a mixture of salts containin an excess of the solid phases of sodium chloride and any form of the normal sodium carbonate except sodium carbonate monohydrate, while warming the mixture to a temperature between 28 and 31 centigrade, whereby suchprepared brine contains from l9% to 21% NazCOz, is saturated with sodium chloride and'is highly supersaturated with respect to sodium carbonate monohydrate, removing undissolved matter from the brine, and then releasing the supersaturation of the clear brine with respect to monohydrateby seeding it with crystals of sodium carbonate monohydrate, maintaining the mixture at a temperature over 24 centigrade for a sufllcient length of time to come to solubility equilibrium with respect to the monohydrate, separatingthe precipitated pure monohydrate from the mother liquor, and washing samesubstantially free from adhering mother liquor impurities.

3. The method of preparing pure sodium car-.

bonate monohydrate which consists in agitating a brine which is saturated with sodium carbonate and sodium chloride and contains also some sodium sulphate with a mixture of salts containing an excess of the solid phase of sodium chloride and of any form of the normal sodium carbonate except the monohydrate, while warming the mixture to a temperature between 28 and 31 0., whereby such prepared brine acquires a content sodium chloride and highly supersaturated with respect to sodium carbonate monohydrate, re-

moving the undissolved matter-from the brine, releasing the supersaturation of the clear brine with respect to sodium carbonate monohydrate to cause it to separate out sodium carbonate monohydrate, maintaining the mixture at a temperature over 24 C. for a sufiicient length of time to come to solubility equilibrium with respect to the monohydrate, separating the precipitated pure monohydrate. from the mother liquor, and washing the same substantially free from mother liquor impurities.

ALEXIS C. HOUGI ITON. 

